Process of treating complex metallic compounds of omicron-hydroxyazo dyestuffs



Patented June 24, 1930 UNITED STATES PATENT- OFFICE ms xnzIxALm AND mus KKMMEBIB, on mnn'nm, GERMANY, ASSIGNORS-TO GENERAL ARIIIINE WORKS, OF DELAWARE PROCESS OF TREATING COMPLEX METALLIC COMPOUNDS OF O-HYDBOXYAZO DYESTUFFS Ho Application fl led larch 24, 1927, Serial No. 178,130, and in Germany March 31, 1926.

We have found that complex metallic compounds of o-hydroxyazo dyestufis, other than the dyestuil obtainable from the diazo compound-of 1-amina-2-naphthol-4=-sulfonic acid 5 and alphanaphthol, may be transformed into products possessing considerably modified properties, by treating them with chemical agents capable of reacting'with, but not destroying the complex dyestufi com ound.

Thus, for example, the, properties 0 these complex metal compounds may be greatly infiuenced by the introduction of 'substituents into the complex dyestuif compounds, or by varying the substituents already present therein. We have found that the stability of the complex metallic compounds of o-hydroxyazo dyestuffs, in particularof the chromium compounds, is such that allreactions which may be applied to the dyestuffs themselves may be carried out wlththe metal compounds without destroying the complex. For example chromium compounds of the said dyestuffs, which also contain nitro groups, can be treated with reducing agents without destroying the metallic complex. Depending on the reducing agents employed, the

nitro roups may, for example, be transforme into amino or azoxy groups, thereby modifying the'shade, the property of producing even, dyeings and the aflinity of the dyestuflt's, Moreover,.complex metallic comounds of o*-hydroxyazo dyestuffs, containing ree amino groups-such as those obtained by i the reduction of-nitro derivatives, as already mentioned, or such 'as can be produced for example from 'aminonaphthol sulfonic acids by alkaline coupling with diazo compoundscan be treated, without injury to the metalliccomplex, with acylating, alkylating or arylating agents, or other agents capable of modifying the amino groups. Acetylation or benzoylation or other acylation usually lightens the shade, and it is possible to obtain in the manner herein mentioned,'for example, acetylated complex chromium compounds, which are dif weight.

ficult, ifnot impossible, (owing to the risk- Several molecules of the complex metallic compounds of o-hydroxyazo 'dyestufi's contaming ammo groups can be linked together by treatmentwith phosgene, by which treat-.1

NEW YORK. N. Y., -.A. CORPORATION OF ment especially the afiinity of the dyestuflfs for cotton is increased.

The following examples will further illustrate how the said invention may be carried into practical effect but .theinvention is not limited to these examples. The parts are by E wample 1 47 parts of-the complex chromium compound ofthe azodyestufi prepared by alkaline coupling of diazotized p-chlor-o-aminophenol and with 1-amino-8-naphthol-3.6'- disulfonicacid are dissolved in water, and treated with aboutllii parts of acetic anhydrid. at a temperature of 70- C. A change of tone from greenish-blue to a blue with a reddish tinge occurs; After acetylation is completed the product is salted-out and filtered oil bysuction. It corresponds most probably tothe following ionnula The dyeings produced by the resulting dyestuff on wool have a more reddish shade than those obtainedfrom the original dye'stufl.

Example 2 stirred with 42 parts of crystalline sodium 'sulfid until reduction is complete. The mixture is then neutralized with acid, salted out and filtered. The reaction product correspends most probablyto the following for:

mula

OH H0 Cr I A fast dyestufl:',producin ver even d ein s, is obtained which. dyes vool loluish-gi'ey in weak shadeswhereas the original dyestufi gives violet-brown dyeings on wool.--

The complex metal compounds of many other o-hydroxyazo dyestuffs can be reduced in a similar manner, with not only a change of shade, but also in almost all casesan improvement in the properties of dyeing evenly of thedyestuffs. In the case of dyestuffs containing a plurality of nitro groups, for example picramic acid dyestuffs, one or more i of the nitro groups may be reduced byvary- 1n the amount of the reducing agent, thus inlpencing the dyestufi in various ways at W1 i The aforesaid dyestufiobtainable by reducing the chromium compound of the dyestufl obtained from p-nitro-o-amino-phenolo-sulfonic acid and beta-naphthol can be transformed, by acetylation in the manner described in Example-'1, into a product which dyes wool shades with a more reddish tinge than the unacetylated dyestufi.

' Example 44 parts of the complex chromium compound ofthe nitrated azo dyestuff from l-amino- 2-naphthol-4-sulfonic acid and )3- napthol are dissolved in a small. quantity of water, 20 parts of caustic soda solution (40 B.) being added, followed by {10 parts of grape sugar in concentrated solution. The mixture is stirred for about 30 hours, neu- .tralized with acid and filtered. A 'dyestufi is obtained which gives fast, dark blue shades on'wool. It corresponds most probably'to the following formula:

Example 1;

50 parts of the complex copper compound of the azodyestuif obtainable by alkaline coupling of picramic acid with 1-amino- 8- naphthol-3L6-disulfonic acid, are dissolved in I water and stirred with about 25 parts of shade than the original dyestufl. It corresponds most probably to the following formula: e

Cu l Ewmnple 5 for some time in an aqueous solution with 20 parts of dinitro-chlor-benzene with an addi- "acetic anhydride at a temperature of C. I ,After acetylation is completed, the mixture is i tion of 15 parts of sodium carbonate. The

resulting dyestufi is separated in the usual manner. Itdyes wool fast brown shades.

v Ewample 6 47 arts of the complex chromium 'compoun of the azodyestufi obtainable from amino-8-naphthol-3.6-disulfonic acid by. coupling in an alkaline solution are dissolved in water, diazotized inan acid solution with diazotized 4= nitro-2-amino-phenol and 1- I ion the calculated quantity of sodium nitrite,

boiled-until diazo compound is no longer present, neutralized and salted out or evaporated. The resulting dyestufl containing a hydroxylgroup instead of the amino group of the initial dyestufi dyes more reddish shades than the initial material.

We claim: v 1. The rocess which comprises treating with a re ucing agent a complex metallic compound of an ortho-hydroxy-azodyestuff containing at least one nitro group.

2. The process which comprises treating a complex metallic compound of an ortho-- hydroxy-azo-dyestufi' containing at least one l nitro group with a reducing agent to the corv responding amino compound and acylat ing the resulting product.

3. The process which comprises treating a complex chromium compound of an ortho-' hydroxy-azodyestufil' containing at leastone mtro group with sodiumsulfid until the reduction is complete. I

4. The process which comprises treatin a complex chromium compound of an ort o hydroxy-azodyestuflf containing at least one nitro group with sodium sulfid to the corresponding amino compound and acylating theresultmg product by treating it with acetic anhydride.

5. As a new article of manufacture, the

complex chromium compound corresponding "probably to the formula:

N=N NH:

d) on i I 0:11 i dyeing wool weak bluish grey shades, and obtainable by reducing the complex chromium compound of the. azodyestufi from diazotized p ntroo -aminoph enolo -sulfonic acid and B-naphthol by means of an aqueous solution of sodium sulfid. I

In testimony whereof we have hereunto set our hands. HANS KltZIKALLA. I HANS KAMMERER. 

